EP0819155A4 - Brominated syndiotactic styrenic polymers and method for making and using same - Google Patents
Brominated syndiotactic styrenic polymers and method for making and using sameInfo
- Publication number
- EP0819155A4 EP0819155A4 EP96910522A EP96910522A EP0819155A4 EP 0819155 A4 EP0819155 A4 EP 0819155A4 EP 96910522 A EP96910522 A EP 96910522A EP 96910522 A EP96910522 A EP 96910522A EP 0819155 A4 EP0819155 A4 EP 0819155A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- styrenic polymer
- syndiotactic
- syndiotactic styrenic
- brominated
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims description 34
- 239000000654 additive Substances 0.000 claims abstract description 27
- 239000012429 reaction media Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 239000003063 flame retardant Substances 0.000 claims abstract description 18
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- -1 A1C13 Chemical compound 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- 239000004793 Polystyrene Substances 0.000 claims description 15
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 14
- 229920002223 polystyrene Polymers 0.000 claims description 14
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 6
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 150000003440 styrenes Polymers 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 3
- 229910021576 Iron(III) bromide Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 125000003011 styrenyl group Polymers [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 2
- RPJGYLSSECYURW-UHFFFAOYSA-K antimony(3+);tribromide Chemical compound Br[Sb](Br)Br RPJGYLSSECYURW-UHFFFAOYSA-K 0.000 claims description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 2
- 229910001627 beryllium chloride Inorganic materials 0.000 claims description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims 1
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims 1
- 229910015845 BBr3 Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 25
- 230000031709 bromination Effects 0.000 description 12
- 238000005893 bromination reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000002952 polymeric resin Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 229920003002 synthetic resin Polymers 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229920005669 high impact polystyrene Polymers 0.000 description 3
- 239000004797 high-impact polystyrene Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229910014265 BrCl Inorganic materials 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001123 polycyclohexylenedimethylene terephthalate Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JWVTWJNGILGLAT-UHFFFAOYSA-N 1-ethenyl-4-fluorobenzene Chemical compound FC1=CC=C(C=C)C=C1 JWVTWJNGILGLAT-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004727 Noryl Substances 0.000 description 1
- 229920001207 Noryl Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004954 Polyphthalamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000004957 Zytel Substances 0.000 description 1
- 229920006102 Zytel® Polymers 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920000314 poly p-methyl styrene Polymers 0.000 description 1
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920006375 polyphtalamide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000008257 shaving cream Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
Definitions
- the present invention concerns a new material or additive for use as a flame retardant. More particularly, the present invention concerns a new and improved flame-retardant additive comprising a brominated syndiotactic styrenic polymer and a method of making and using the same.
- Flame-retardant additives and methods of making and using the same are well-known in the prior art. Flame-retardant additives are added to many polymers during processing so as to render the finished product made with such polymers resistant to ignition.
- One class of flame retardants that is used extensively in industry comprises halogenated polymers of styrenic monomers. This class of materials is utilized to impart flame-retardant properties to a broad range of polymeric resins such as, for example, polyamides, polyesters such as PET and PBT, polyolefins and styrenic polymers such as HIPS, ABS, SAN, etc.
- An example of a commercially successful product of this class is a brominated polystyrene flame-retardant additive sold by the Ferro Corporation of Cleveland, Ohio, under the trademark PYRO-CHEK ® 68PB.
- U.S. Patent No. 4,352,909 which is owned by Ferro Corporation discloses a method for producing a brominated polystyrene flame-retardant additive such as PYRO-CHEK 68PB. Additional examples of references that disclose methods for producing brominated styrenic polymers are Naarmann et al. , U.S. Patent No. 4,143,221, Diebel et al. , U.S. Patent No. 4,200, 703 and Lindenschmidt et al. , U.S. Patent No. 4,360,455. Prior art methods of brominating styrenic polymers to a useful degree, as taught in the above mentioned patents, all teach the step of putting the styrenic polymer into solution by use of a solvent during the bromination step.
- Nakano U.S. Patent No. 5,200,454 concerns a flame- retardant resin composition wherein the host or base polymeric resin comprises syndiotactic styrenic polymer.
- Nakano '454 also talks briefly of adding halogenated syndiotactic polystyrene to syndiotactic polystyrene polymeric resin.
- Nakano '454 does not provide any insight whatsoever into how to produce the halogenated syndiotactic polystyrene.
- the commercial trend over the last ten years has been to utilize host polymeric resins displaying increasingly higher working temperatures .
- the present invention meets the challenges created by this trend by providing a flame- retardant additive that is well suited for use in today's high temperature polymeric resins. Further, the present invention provides a novel method of producing brominated syndiotactic styrenic polymer additives that display unique and improved properties as compared to additives made using conventional methods .
- the present invention provides a new and improved flame retardant additive comprising brominated syndiotactic polystyrene and a novel method for using such additive.
- the flame-retardant additive of the present invention provides for better color and improved thermal stability as compared to the use of conventional brominated polystyrene in host polymeric resins .
- the flame-retardant additive of the present invention comprises brominated syndiotactic polystyrene having a melting temperature in excess of about 325°C and a degradation temperature in excess of about 325°C.
- the additive is preferably produced utilizing an inert reaction medium that is incapable of dissolving to any appreciable degree syndiotactic polystyrene at ambient temperature and pressure.
- the invention further provides a method of flame retarding host polymeric resins using the brominated syndiotactic polystyrene of the present invention and a method for making the brominated syndiotactic polystyrene of the present invention.
- the method of the present invention does not include the step of dissolving the syndiotactic styrenic polymer.
- Prior art methods of brominating styrenic polymers such as polystyrene to a useful degree (i.e., over 15% by weight bromine) all teach the step of putting the styrenic polymer such as polystyrene into solution by use of a solvent before initiation of the bromination step. Contrary to the suggestions of the prior art, applicants have discovered that when brominating syndiotactic styrenic polymers it is not desirable to form a solution by use of a solvent prior to brominating.
- the method of making the brominated syndiotactic polystyrene comprises the steps of providing a source of syndiotactic styrenic polymer, providing a source of reaction medium which does not dissolve the syndiotactic styrenic polymer to any appreciable degree at ambient temperature and pressure, providing a source of brominating agent, providing a Lewis acid catalyst, mixing the syndiotactic styrenic polymer with the reaction medium and the Lewis acid catalyst, and reacting the syndiotactic styrenic polymer with the brominating agent to produce a flame retardant comprisingbrominated syndiotactic styrenic polymer.
- syndiotactic styrenic polymer is suspended in an inert reaction medium and reacted with a brominating agent in the presence of a Lewis acid catalyst to produce brominated syndiotactic styrenic polymer of the general structure:
- the syndiotactic styrenic polymer for use in the process according to the invention is a styrenic polymer having mainly the syndiotactic configuration.
- the styrenic polymer having mainly syndiotactic configuration means a styrenic polymer having a configuration that with respect to a main polymer chain comprising a carbon-carbon bond, and phenyl groups or substituted phenyl groups, has substituents that are positioned alternately on the opposite sides of the plane of the main polymer chain.
- the styrenic polymer having mainly syndiotactic configuration to be used in the present invention includes polystyrene, poly(alkylstyrene) wherein the substituent is on the aromatic ring, poly(halogenated styrene) , and poly(alkoxystyrene) .
- at least 60% by weight, and more preferably at least 75% by weight of the styrenic polymer resin displays a syndiotactic configuration.
- Typical examples of the poly(alkylstyrene) are poly(methylstyrene) and poly(ethylstyrene) .
- poly(halogenated styrene) are poly(chlorostyrene) , poly(bromostyrene) , poly(fluorostyrene) and the like.
- poly(alkoxystyrene) are poly(methoxystyrene) , poly(ethoxystyrene) and the like.
- syndiotactic styrenic polymers are polystyrene, poly-p-methylstyrene, poly-ortho-methylstyrene, poly-p-tert-butylstyrene, poly-p-chlorostyrene, poly-ortho- chlorostyrene and poly-p-fluorostyrene.
- the styrenic polymer to be used in the present invention varies in molecular weight.
- the styrenic polymer to be used in the present invention is not critical in a distribution of molecular weight, and those having various distributions of molecular weight can be used.
- the weight average molecular weight of the syndiotactic styrenic polymer is usually from about 200,000 to about 550,000 although it is not limited thereto.
- the styrenic polymer having mainly syndiotactic configuration can be prepared, for example, by polymerizing a styrenic monomer (corresponding to the above styrenic polymers) in the presence of a catalyst such as a catalyst comprising a titanium compound and an aluminum organo compound.
- a catalyst such as a catalyst comprising a titanium compound and an aluminum organo compound.
- syndiotactic styrenic polymers are incorporated herein by reference for their teachings of how to produce syndiotactic styrenic polymers. Applicants believe that the present invention is best practiced using powdered, as compared to a conventional pelletized form. More particularly, the syndiotactic styrenic polymer utilized preferably has an average particle size of from about .1 to about 10 microns.
- Lewis acid catalysts which are suitable for the process according to the invention and are used in amounts of from about .10% to 40% by weight, preferably from about .20% to 20% by weight, based on the weight of styrenic polymer used or charged, include, for example, iron- (III) chloride (FeCl 3 ) , SbCl 3 , SbCl 5 , iron- (III) bromide (FeBr 3 ) , aluminum- (III) chloride (A1C1 3 ) , aluminum- (III) bromide (AlBr 3 ) , boron- (III) bromide (BBr 3 ) , boron- (III) chloride (BC1 3 ) , copper- (II) bromide (CuBr 2 ) , SbBr 3 , TiCl 4 , TiBr 4 , SnCl 2 , SnCl 4 , AlBr 3 , BeCl 2 , CdCl 2
- the Lewis acid catalysts exhibit different levels of activity. Moisture, methanol and other materials that complex with the catalyst affect the level of activity of any given catalyst.
- SbCl 3 less than 5% of the catalyst SbCl 3 can be used to achieve tribromination if the system is essentially dry.
- An "essentially dry” or “substantially anhydrous" system or reaction mixture is one in which all of the reaction medium employed has been azeotropically distilled to remove water. Typically this produces a moisture content of 0.002% or less based on the use of an ethylene dichloride reaction medium.
- Other components are purchased or made up to be as dry as feasible when employing a catalyst such as SbCl 3 . Comparable bromination results cannot be obtained if higher levels of moisture are present.
- Bromine and bromine chloride may be used as the brominating agent.
- Bromine chloride is the preferred brominating agent for use in practicing the preferred mode of the invention when SbCl 3 or a catalyst of similar activity is utilized. As compared to the use of bromine per se, bromine chloride is generally preferred.
- the reaction medium that is employed in the process is critical.
- the reaction medium must not dissolve the syndiotactic styrenic polymer to any appreciable degree at standard bromination temperatures and ambient pressures (i.e. , 70°F and 1 atmosphere) .
- the suitable reaction medium is one in which the order of the syndiotactic styrenic polymer is not substantially altered at standard bromination conditions.
- reaction media that are suitable for use in the present invention when syndiotactic polystyrene is utilized include, for example, 1, 2-dichloroe hane, chloroform, carbon tetrachloride, methylene bromide, l,2-dibromoethane, 1, 1, 2-trichloroethane, and ethylene dichloride (EDO and mixtures of such media.
- Materials that are not preferred for use with the present invention when syndiotactic polystyrene is utilized include, for example, 1, 1, 2, 2-tetrachloroethane for it will dissolve the syndiotactic polystyrene and produce a solution.
- the syndiotactic styrenic polymer and a suitable reaction medium are first introduced into a reaction vessel apparatus, which may, for example, be a stirred vessel or other mechanically agitated vessel or container.
- a reaction vessel apparatus which may, for example, be a stirred vessel or other mechanically agitated vessel or container.
- One of the conventional bromination catalysts is then added.
- the mixture is stirred or mixed and the desired amount of brominating agent is run in at from about -30°C to about 50°C, preferably from about -20°C to about 45°C.
- excess brominating agent is neutralized by a reducing agent such as sodium bisulfite.
- the product may be isolated utilizing any one of several conventional isolation techniques such as, for example, flashing of the reaction medium by the addition of the reaction mixture to hot water.
- thermoplastics for such flame retarding include, for example, polyamides such as polyphthalamides, Nylon 6, Nylon 6,6, Nylon 4,6 and Nylon 6,12, polyesters such as polyethylene terephthalate (PET), polycyclohexylene dimethylene terephthalate (PCT) and polybutylene terephthalate (PBT) , polymers and copolymers of ⁇ -olefins such as polyethylene, polypropylene, polybutene, poly-4-methyl pentene-1, propylene/ethylene copolymers, copolymers of 4-methyl pentene-1 with linear ⁇ -olefins containing 4 to 18 carbon atoms, and ethylene/vinyl acetate copolymers, and styrenic polymers such as polys
- thermoplastics of the brominated syndiotactic styrenic polymer additive and of synergistic agents which may or may not be used, as well as the incorporation of further additives which may be employed, can be carried out by suitable conventional mixing processes, for example in extruders, Banbury mixers, two roll mills or other plastic processing equipment. Self-extinguishing moldings and profiles can be produced, by injection-molding or extrusion, from the mixtures with thermoplastics prepared using the additive product or blended product resulting from the process according to the invention.
- Effective amounts of the brominated syndiotactic polystyrene of the present invention are generally present from about 2% to about 40% by weight, preferably from about 5% to about 35% by weight of the total final composition (i.e., the host or base polymeric resin(s) and the brominated syndiotactic polystyrene, fillers, other additives, etc.) .
- the blends of the present invention can contain various conventional additives in conventional amounts as known in the art. For example, additives such as UV light inhibitors or stabilizers, lubricant agents such as calcium stearate, antimony base synergists, heat stabilizers and other additives .
- Brominated syndiotactic polystyrene made in accordance with the present invention displays a melting temperature
- brominated syndiotactic polystyrene made in-solution displays a softening point well below 300°C and it has well over 350 ⁇ ppm (and typically over 6000ppm) halogen located on the backbone of the polystyrene as measured in HBr equivalents .
- Halogen on the backbone of the polystyrene is very undesirable.
- the halogen is preferably located on the ring of the polystyrene. Backbone halogenation leads to numerous problems such as poor thermal stability for the end user.
- Brominated syndiotactic polystyrene made in accordance with the present invention also displays a thermal stability of less than about 1500ppm HBr by the GE thermal stability test as compared to in-solution made brominated syndiotactic polystyrene which displays a thermal stability of over about 6000ppm HBr by the GE thermal stability test. Further, it has been noted that brominated syndiotactic polystyrene made in accordance with the present invention displays a melting point and it is non-amorphous and thus it displays at ambient conditions a noncrystalline order.
- brominated syndiotactic polystyrene made in-solution is amorphous in nature and it does not display a melting point.
- a noncrystalline order is well documented and discussed beginning at Volume 4, page 449, of the Encyclopedia of Polymer Science and Technology ® 1966.
- An additive having noncrystalline order that displays various beneficial properties can only be obtained by using the process of this invention.
- Example I Into a 5L resin flask equipped with a mechanical stirrer, thermometer, spiral condenser, and a 500mL jacketed pressure equalized addition funnel was placed 300.6g (2.886 mole based upon molecular weight of a styrene repeating unit) powdered syndiotactic polystyrene having a weight average molecular weight of 450,000 and 2100mL of 1,2 dichloroethane (EDC) . To the stirred mixture was added 15g (0.06576 mole) antimony trichloride (added as a solution in EDC - 0.4g/mL) and the mixture was cooled to 15°C.
- EDC 1,2 dichloroethane
- Bromine chloride 1125.Og (9.75 mole) (added as a solution in EDC - 50% w/w) was added to the flask at a rate of 3.25 moles/hr BrCl while keeping the bromination temperature at approximately 20°C ⁇ 2°C. After the addition of the BrCl was completed, the reaction mass was held at 20°-25°C for an additional three hours (total contact time is six hours) .
- Aqueous sodium bisulfite (620g of 20% NaHS0 3 ) was added at such a rate as to not exceed 35°C.
- a weight of deionized water equal to the weight of the aqueous sodium bisulfite used, was added to the mixture.
- the entire mass was stirred for an additional ten minutes, and then filtered to yield a white solid.
- the white solid was washed three times by slurrying each time with 2500mL of fresh deionized water for two hours, and filtering. During the second and third washes, the product exhibited a creamy/shaving cream like texture.
- the solid was charged along with six liters of deionized water to an appropriately sized resin flask equipped with a mechanical stirrer, distillation head, condenser, receiver, and heating mantle. The resulting slurry was heated gradually whereupon the EDC/water azeotrope was removed from the system. Ultimately the slurry was heated to 100°C and was held at that temperature for two additional hours.
- the pH of the slurry was adjusted from 4 to 8 by the incremental addition of 10% aqueous NaOH. Propanol was added to the slurry to serve as a wetting aid and the slurry was then stirred at 80°C for four hours.
- the product was collected by filtration, washed on a filter with 4L of hot deionized water and then 2L of cold deionized water. The product was vacuum dried at 100°C at 5-
- Example III Utilizing the brominated syndiotactic polystyrene (BrSPS) of Example I, the following flame-retarded blends were produced using a twin screw extruder. Oxygen Index For
- PET-DuPont Ryriite 530 83PET/4Sb;0,/13BrSPS 20.10 30.60 V- -0
- Example IV Into a dried 100 gallon glass-lined reactor equipped with three-bladed retreating blade agitator, dip tube, H-style finger baffle with thermowell, condenser, receiver and scrubber are charged with stirring 421.0 pounds dry 1,2- dichloroethane (EDC), 47.5 pounds (0.4561 pounds-moles based on styrene repeating units) powdered syndiotactic polystyrene and 2.399 pounds (0.01052 pounds-mole) antimony trichloride dissolved in 0.75 gallon dry 1, 2-dichloroethane. The mixture is stirred and cooled to 16°C.
- EDC 1,2- dichloroethane
- 47.5 pounds (0.4561 pounds-moles based on styrene repeating units
- powdered syndiotactic polystyrene and 2.399 pounds (0.01052 pounds-mole) antimony trichloride dissolved in 0.75 gallon dry 1, 2-dichlor
- Bromine chloride 180.0 pounds (1.560 pounds-mole) , is added to the mixture at a rate of 1 lb/min, while keeping the reaction temperature between 20°- 25°C. Approximately 2.75 hours into the bromine chloride addition, the mixture thickened into a pasty, but stirrable, mass. After the three-hour bromine chloride feed, the mixture is stirred for another 9 hours, maintaining the temperature at 20°-25°C. Aqueous sodium bisulfite, 400 pounds of 10% w/w, is then pumped in to neutralize the unreacted bromine chloride, followed by pH adjustment of the reaction mixture to pH 7 with 310 pounds 10% w/w aqueous sodium hydroxide. The crude product was then collected via centrifuge.
- the solid was washed three times by slurrying each time in the reactor with 500 lb fresh water and centrifuging. After the third wash, the solid was charged back to the reactor, 500 pounds fresh water added and the mixture was heated with stirring to about 77°C, whereupon the EDC/water azeotrope was removed from the system. The resulting slurry was then gradually heated to 100°C and held there for 2 hours. The slurry was then cooled and centrifuged to collect the solid product wet cake.
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Abstract
Description
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Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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US41809795A | 1995-04-06 | 1995-04-06 | |
US418098 | 1995-04-06 | ||
US08/418,098 US5616656A (en) | 1995-04-06 | 1995-04-06 | Method for making brominated syndiotactic styrenic polymers |
US418097 | 1995-04-06 | ||
PCT/US1996/003943 WO1996031578A1 (en) | 1995-04-06 | 1996-03-22 | Brominated syndiotactic styrenic polymers and method for making and using same |
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EP0819155A1 EP0819155A1 (en) | 1998-01-21 |
EP0819155A4 true EP0819155A4 (en) | 1998-08-19 |
EP0819155B1 EP0819155B1 (en) | 1999-09-22 |
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EP96910522A Expired - Lifetime EP0819155B1 (en) | 1995-04-06 | 1996-03-22 | Brominated syndiotactic styrenic polymers and method for making and using same |
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EP (1) | EP0819155B1 (en) |
JP (1) | JPH11503475A (en) |
AU (1) | AU5369496A (en) |
DE (1) | DE69604388T2 (en) |
WO (1) | WO1996031578A1 (en) |
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US5723549A (en) * | 1996-06-14 | 1998-03-03 | Ferro Corporation | Process for the preparation of brominated polystyrene having improved color characteristics |
US5637650A (en) * | 1996-06-14 | 1997-06-10 | Ferro Corporation | Brominated polysytrene having improved thermal stability and color and process for the preparation thereof |
EP1013671B1 (en) * | 1998-06-23 | 2001-11-28 | Industrial Technology Research Institute | Functionalized syndiotactic styrene/para-alkylstyrene copolymer |
US6992148B2 (en) | 2003-12-31 | 2006-01-31 | Albemarle Corporation | Recovery of antimony catalyst residues from bromination reaction mixtures |
BRPI0620898A2 (en) * | 2005-12-21 | 2011-11-29 | Albemarle Corp | preparation of brominated styrene resins or polymers |
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US4352909A (en) * | 1980-08-20 | 1982-10-05 | Ferro Corporation | Process for the bromination of polystyrenes |
US5200454A (en) * | 1988-01-14 | 1993-04-06 | Idemitsu Kosan Company Limited | Flame-retardant resin composition |
US5109068A (en) * | 1988-08-31 | 1992-04-28 | Idemitsu Kosan Co., Ltd. | Styrene-based polymer composition, stretched molding thereof and process for producing the same |
US5321122A (en) * | 1989-07-28 | 1994-06-14 | Idemitsu Kosan Co., Ltd. | Process for purification of styrene polymer |
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1996
- 1996-03-22 DE DE69604388T patent/DE69604388T2/en not_active Expired - Fee Related
- 1996-03-22 WO PCT/US1996/003943 patent/WO1996031578A1/en active IP Right Grant
- 1996-03-22 JP JP8530331A patent/JPH11503475A/en active Pending
- 1996-03-22 AU AU53694/96A patent/AU5369496A/en not_active Abandoned
- 1996-03-22 EP EP96910522A patent/EP0819155B1/en not_active Expired - Lifetime
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DE69604388D1 (en) | 1999-10-28 |
WO1996031578A1 (en) | 1996-10-10 |
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AU5369496A (en) | 1996-10-23 |
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